Heterocyclic alkylamines as accelerators for photographic developers



Patented July 29, 1.952

HETEROCYCLIC ALKYLAMINES AS AC- CELERATORS FOR PHOTOG'RAPHIU- 'zDEVELQPERS Ivy V. Runyan, Binghamton, N. Y., assignor to M 'l General Aniline & Film Corporation, New York,

I No Drawing.

12 Claims.

This invention relates to photographic developers and particularlyto nuclear aminoalkyl substituted heterocyclic compounds as accelerators for photographic developers.

It is well knownthat various amines, such as primary and secondary alkyl and alkylene amines containing from, 3.1107. carbon atoms, may be added to photographiczblack .and white and color developing solutions for the purpose of increasing the rate of development. ,In other words, these amines accelerate the development so as to cause the developing agent to form the image (silver or color image) :morerapidly than is possible withoutthe presence "of such amines.

Although developing solutions containing such amines cut the developing time to 12-15 minutes, such period is still unsatisfactory where large scale operations are involved, as in commercial processing where-time" 1510f theiepssence.

It is also knovvn that-nitrogenous heterocyclic bases, such as piperidine, pyrr olidine, morpholine, piperazine, lysidine and the like, which, when present in color forming photographic developers in an amount ranging from about 0.5 gram to 4 grams per liter, make it possible to obtain images having a harmoniousgradatio'n,reduced contrast, and satisfactory brilliance. While these bases energize weak color forming photographic developers to the extent that pictures of improved appearance are obtained, they do not, however, permit a reduction in development time, nor do they permit the development of pictures having an overall increased contra'st. Moreover, the use of these heterocyclic bases in color developers may lead to skin. irritations and sometimes eruptions when color development of the film is done with bare hands.

It is, therefore an.objectofthe present invention to provide a black and white and color developer having, an increased :ra'te oil-development. so that, developing time;is:asubstantially:.:decreased to less-than {half or the normalitimeswithout loss of ,Q l ira -a peed.-

; I o :i

A;-fu rther;- object is, to providennuclear amino allrylsubstituted :heterocyclic' compounds as. -5acer iq r ior hq eeranh de e pers w ich re less toxic than the alkylam-ines; and heterocyclic bases of-the-prior art. 1 r H 1 e 1 e S;.wi a-s pe ihei il arierz v VThe.foregoingobjects'az e-accomplished Joy-addin'gl'a nuclear. .aminoalkyl substituted. heterocyclio compound to theusuallblacki and white developer and 'to a'color forming developer in which aprimary ,aromatic amine is used as. thedeveloping agent. ""It 'has'"'been found that in developing :N'.sY., a corporation of Delaware Application November 16, 1949, w L Serial No. 127,779

color images in multicolor photographic layers containing color formers fast to diffusion, as dis closed in United States Patents 2,178,612, 2,179,228, 2,179,234, 2,179,238-9, 2,179,244, 2,186,719, 2,186,851, 2,186,852, 2,186,732-3-4,

2,186,849, 2,200,306, 2,280,722, 2,292,575, 2,303,928, and 2 ,307 ,399,, with;;a: color develop er containing a nuclear .aminoalli'yl 'sub'stitutd heterocyclic compound, thedevelo'ping' time is cut from 20-30 minutes to 2-10 minutes. All of the layers are simultaneously developed gandqthe dye images formed are of excellent quality.

The developing time with black and white developers, for instance, solutions of hydroquinone and Metol (p-methylaminophenol sulfate) and the like, is alsocut by more thanhalf without causing fog when suchi solut'ions contain a nuclear aminoalkyl substituted heterocyclic compound.

The accelerators employed in accordance with the present invention are heterocyclic compounds containing an aminoalkyl group of not more than 3 carbon atoms substitutes :.(i. e., for a hydrogen atom) in the nucleus of such compounds having from one to two 5- to-fif-membered mutually combined rings in the nucleus in "which one of the rings has one to two hetero atoms of which one is a member of the group consisting of N, O and S, the second being nitrogemfand" the remaining members of the nucleus being carbon atoms.

The following are examples of such nuclear aminoalkyl substituted heterocyclic compounds:

6-(B-a.minoetl1yl)-2-methylbenzimldazole (German Patent 294,085 Beil. 25, 638) NH-o-om-pmNm O\ N ,oH 5-(s-amautymmmizon (histamine) (Ber. 40, 3694) 6-.(Beminbethyl)'benzimidazole (Beil. 25, I SupplemggigggeafiE'l, German Patent I D I N C O if N cHl-oH onPDH, 5-aminomethyl LmefliylimidaZoIone- (4) (Ber. 1:1, 2549) 3-(B-aininoethyl)1ndol (J'. Chem. Soc. 99, 2 72, 1911) 3- ('y-amlnopropyl) piperidone-Z (Hex-.27, 9 80 (1894)) V 1- 'y-aminopropyl) piperidine (Ber. 27, 2177) 1 (fl-aminoethynplperidine (Ber, 24, 1121) 2-amlnomethylpiperidine (Ann. 493. -32) cm-oH-om 2- (B-aminopropyl) pyridine (Ber. 38. 3334) Y CHI 2-amlnomethyl-4,5-dlmethylpyridine (J. A. as. 11,332)

2- (B-aminopropyl) piperldine (Ber. 38, 3340) Furfurylamine' i (Ber.;20, 309) 1 2- a-amlnoethyl) thiophene l 0. 1700) (Ber. 2

v 1 {HO Ht") LL-CH2NHB (Ber. 36,

CH-S v HgNCHmCHm T (5.06115 2- (a-aminoethyl) coumarone 4-(B-amlnoethyl)-2-plienylthiazolone (1. A. C. S. 52, 3726) r s HgNCHlCL CJCoHs 4-aininomethyl-2-phenylthiazoline (Rec. Trav. Chim. 49, 1066) 4- [B-amlnoethyl] -glyoxaline (J. A. C. 8.40. 1717,.191'8) N CH$CH2NHZ CH1 CH3 sa/ a 3-(fl-aminoethyl)morpho1ine (Marshall Rev. 2, 8 (1939) Cummings and Todd) i f B-aminomethylmorphollne HO 'QH,

\N/U -efigNF-Hi H s V V V 2-aminomethylpyrrole- (C.;A.,l21; .583), r, These nuclear aminoalkylsubstituted 'hetero cyclic compounds are soluble 1 in water and in alkaline developers, and may be used in specified amounts. Their solubility in-water-and 'in'alkaline developers can be made appreciable bycmverting the base into a salt such' as, for example, the sulfate, hydrochloride, carbonate, or carbamate, The sulfate and hydrochloride salts are readily prepared by the'addit'ionof; a. stoichiometrical quantity of dilut e'fsulfuric acid and hydrochloric acid, respectively, and the carbonate or carbamate is prepared by introducing CO2 ]into an alcohol, benzene or ethersolution of the ase. l .7 v The most useful concentrations in black and white developers range from about 1 rain to about 1'0 'grains per uter" of developr. 111 "color developers the most useful concentrations range from about 2 grams to 5 grams per liter. Concentrations greaterythan lOgrams per liter of color developer have the tendency to distort the color balance of the color film. v

In developing color images in; multicolor photographic layers containing color former's'fast to diffusion with a color developer containing a nuclear aminoalkyl substituted heterocyolic compound, the developing time is out from 20-30 minutes-to 2-10minutes'. All'of'the layers are simultaneously developed, and the dye' images formed are of excellent quality. I

The developing time with black and white developers. forinstance, solutions of hydroquinone and p-monomethylaminophenol sulfate and the like, is also cut to about one-half without causing fog when such solutions contain a nuclear aminoalkyl substituted heterocyclic compound.

As illustrative of developing solutions containing such nuclear aminoalkyl substituted heterocyclic compounds, the following are given.

Example I Sodium hexarnetaphosphate-- egrams ;l.'0 p-Methylaminophenol sulfate do 3.0 Sodium sulfite (anhydrous). do 50.0 I-Iydroquinone do 6.0 Sodium carbonate (monohydrate) do 40.0 Potassium bromide do 2.0 Sodium thiocyanate do 2.0 Potassium iodide d'o 0.0035 Furfurylamine e e do l 4.0 Water to make liter 1 The foregoing developer on five minutes development at 20 C. of the usual black and white roll film gives a negative of good density and gradation after fixing and washing. The time requiredto develop the same film in the same solution but containing no furfurylamine ranges from to minutes.

The foregoing developing solutions containing the furfurylamine develops up to 1 5-2 stops more speed in about 14 minutes as compared to the same developing solution containing no furfurylamine. I

Eaiwmple II The following developer requires minutes at 20 C. to give a satisfactory degree of color development for color paper:

Sodium hexametaphosphate grams 1.0 Sodiumsulfite (anhydrous) do 2.5 p-Amino-di (p-hydroxyethyl) aniline sulfate d-o 8.0 Sodium carbonate (monohydrate) do 100.0 I-Iydroxylamine hydrochloride do 1.0 Potassium bromide do 1.0 Water to make liter 1 By the addition of 4 grams of 5-aminomethyll-methylimidazolone [4] to the foregoing solution, a color paper of excellent color rendition is developed in about 10 minutes. Without the presence of said amine at least 30 minutes is required to give an acceptable print. Increasing the concentration of the amine further reduces the time of development.

The color photographic multilayer element utilized in the foregoing example consists of an ing primaries yields-the color-picture.

6. integral tri-p'ack emulsion coatedon either the usual paper base, or a clear cellulose acetate or nitrate film base, or in some cases an opaque white film base. Each "of the emulsion layers is sensitized toone of the primary colors of light, namely, blue, green, and red. The top layer is blue sensitive. Afilter layer, yellow in color and blue absorbingg' li'es under the top layer. Below this filter'l'ayer lies a green sensitive emulsion layer} and-below this ared sensitive emulsion layer; Each of-the three silver halide emulsion layers contains 'dye' forming compounds which unite during thef-development of a silver image inan aromaticamine developing agent to form a 'dyewith the oxidation product of the developing agent. As silver is-a-lso formed during development,- it must 'be removed after color development by treatment in a bleach, followed by bath of sodium th-iosul'fate, as is well known in the art. A yellow dye is formed in the blue sensitive emulsion; a magenta dye is formed in the green sensitive emulsion; and a cyan dye is formed in the red sensitive emulsion. The'combination of the dye ir'nages from these three print- Suitable methods forthepreparation of multicolor emulsion layers have been described in the literature relating tocolor photography, and are, therefore, not described here. i

I jEa'zample III' A color developersimilar to Example II but prepared with '5 grams-per liter of p-aminoethylffi-hydroxyethyll'aniline sulfate, 1 and containing 4 grams of JZ-aminOmethylthiQphene developed a multilayer color film of the reversal type, containing a color former fas-tto diffusion, in about 12 minutes, at 20 C. whereas without the Z-aminomethylthiophen'e the color film is too low in maximum density for acceptablereproduction after 25 minutes. 1

The: above examples are to be regarded as merely illustrative of :the invention and not in any sense restrictive. It will be obvious to those skilled in the art that many modifications, such as substituting equivalent materials and varying the proportions of the materials used, are within the spirit and scope of the invention. The scope,

therefore, of the invention is to be limited solely by the following claims.

I claim:

1. An alkaline photographic developer for silver halide emulsions comprising an aromatic silver halide developing agent and a nuclear aminoalkyl substituted heterocyclic compound, the nucleus of which is selected from the group consisting of one 5- to 6-membered ring and two 5- to G-membered rings fused to each other one of said rings containing from 1 to 2 hetero atoms of which one is a member of the group consisting of N, O and S and the other is nitrogen,

thiophene.

7 halide developing agent and aminomethyl-1- methylamidazolonebl] 7 4. An alkaline photographic developer for silver halide emulsions comprising an aromatic silver halide developing agent and Z-aminomethyl- 5. In the development of a photographic negative, the step comprising the development of an exposed silver halide emulsion in an alkaline developer containing an aromatic silver halide developing agent for said emulsion and a developing accelerator, consisting of a nuclear aminoalkyl substituted heterocyclic compound, the nucleus of which is selectedfrom the group consisting of one 5- to fi-rnembered ringand two 5-- to G-membered rings fused to each other, one of said ringscontaining from 1 to 2 hetero atoms of which one is a member of the group consisting of N, O and S and theother is nitrogen, the remaining members of the nucleus being carbon atoms and the remaining nuclear substituents being ,selected :from the class consisting of hydrogen, keto-oxygen, unsubstituted lower alkyl and unsubstituted monocyclic aryl hydrocarbon groups, and the nuclear aminoalkyl substituent group of which contains not more than 3 carbon atoms, and the salts of said amines.

6. In the development of a photographic negative, the step comprising the development of an exposed silver halide emulsion in an alkaline developer containing an aromatic silver halide developing agent for said emulsion and a developing accelerator consisting of 'furfurylamine.

'7. In the development of a photographic negative, the step comprisingthe development of an exposed silver halide emulsion in an alkaline developer containing an aromatic silver halide developingagent for said emulsion and a developing accelerator consisting of 5-aminomethyl-lmethylimidazolone [4] 8. In the development of a photographic negative, the step comprising the development of an exposed silver halide emulsion inan alkaline developercontaining an aromatic silver halide evelop septi sai e u s o nd rl v p-v ing -,accele rato consisting; of 2-aminomethylthiophene p 'f 9. A colorforming photographic developer m ris n a pr m r aro t i e ping agent and a. nuclear aminoalkylsubstituted heterocyclic compound, the nucleus of which is selected from:the group consisting of one 5- to fi-membered ringand two 5- to G-membered rings fused to each other,- one; of said ringscontaining from l to 2 hetero atoms of which one is a member ofthe group consisting of N O and S and the other is nitrogen, the remaining members of the-nucleusbeing carbon atoms and theremaining nuclear substituents being selected from theclass consisting of hydrogen, keto-oxygen, unsubstituted lower alkyl' and unsubstituted monocyclic-; aryl hydrocarbon groups, and the nuclear aminoalkyl substituent group of which contains not more than 3 carbon atoms, and the salts of said amines.

10. A color forming photographic developer comprising a primary aromatic amino developing agent and furfury-lamine.

11. A color forming photographic developer comprising a primary aromatic amino developing agent and s-aminomethyl 1 methylimidazolone[4l.

12. A color forming photographic developer comprising a primary aromatic amino developing agent and 2-aminomethylthiophene.

' IVY V. RUNYAN.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS 

1. AN ALKALINE PHOTOGRAPHIC DEVELOPER FOR SILVER HALIDE EMULSIONS COMPRISING AN AROMATIC SILVER HALIDE DEVELOPING AGENT AND A NUCLEAR AMINOALKYL SUSBTITUTED HETEROCYCLIC COMPOUND, THE NUCLEUS OF WHICH IS SELECTED FROM THE GROUP CONSISTING OF ONE- TO 6-MEMBERED RING AND TWO 5TO 6-MEMBERED RINGS FUSED TO EACH OTHER ONE OF SAID RINGS CONTAINING FROM 1 TO 2 HETERO ATOMS OF WHICH ONE IS A MEMBER OF THE GROUP CONSISTING OF N, O AND S AND THE OTHERIS NITROGEN, THE REMAINING MEMBERS OF THE NUCLEAR BEING CARBON ATOMS AND THE REMAINING NUCLEAR SUBSTITUENTS BEING SELECTED FROM THE CLASS CONSISTING OF HYDROGEN, KETO-OXYGEN, UNSUBSTITUTED LOWER ALKYL AND UNSUBSTITUTED MONOCYCLIC ARYL HYDROCARBON GROUPS, AND THE NUCLEAR AMINOALKYL SUBSTITUTENT GROUP OF WHICH CONTAINS NOT MORE THAN 3 CARBON ATOMS, AND THE SALTS OF SAID AMINES. 